Process for preparing polymers of vinyl monomers with narrow molecular weight distribution by controlled free-radical polymerization

ABSTRACT

Processes for preparing polymers of vinylic monomers where polymerization is conducted in the presence of free-radical initiators and electron donors.

The present invention relates to processes for preparing polymers of vinylic monomers.

The present invention also relates to the use of the polymers obtainable in such processes for preparing moldings.

BACKGROUND OF THE INVENTION

Free-radical polymerization is the most widely applicable technique for polymerizing vinylic monomers. It permits the polymerization of a multiplicity of monomers varying in structure, functional groups and polarity. The copolymerization of different monomers with one another is also possible. Owing to unavoidable side reactions such as chain transfer, disproportionation, recombination or elimination, however, it is very difficult to control the molecular weight distribution. Normally, polymers having a polydispersity index PDI of 2.0 or more are obtained. PDI is defined as ##EQU1## where M_(w) is the weight-average and Mn the number-average molecular weight.

A process which has long been known for preparing polymers with a narrow molecular weight distribution is that of anionic polymerization. However, it is only useful with a limited number of monomers. Apolar monomers, such as styrene or butadiene, can be polymerized anionically. In the case of polar monomers, such as n-alkyl acrylates, for example, anionic polymerization is very difficult. Moreover, anionic polymerization requires highly pure monomers and solvents, and the complete exclusion of atmospheric humidity.

Another method of preparing polymers of narrow molecular weight distribution is that of controlled free-radical polymerization, sometimes also called "living" free-radical polymerization, which is described, for example, in M. K. Georges et al., Trends in Polymer Science, Vol. 2, No. 2 (1994), pages 66 to 72. The fundamental strategy of this method consists in temporarily blocking and then reactivating, in a controlled manner, the reactive free-radical chain ends of a growing polymer chain. The dynamic equilibrium between active and dormant form leads to a low steady-state concentration of free polymer radicals.

A variety of techniques are available for blocking and stabilizing the free-radical chain end. They employ stable free radicals and/or metal salts.

For instance, it is known to use "iniferters", i.e. free-radical generators which both free-radically initiate a polymerization and terminate the chain end by combination. Examples of photochemically activated iniferters, such as dithiocarbamates, are described in T. Otsu et al., Eur. Polym. J., Vol. 25, No. 7/8 (1989), pages 643 to 650. These photochemical iniferters, however, are very expensive compounds, and photochemically initiated polymerization is highly uneconomic in industrial practice. Furthermore, the polydispersity index is very high in some cases. There are also thermal iniferters, such as tetramethylene disulfides, which are described, for example, in K. Endo et al., Macromolecules, Vol. 25 (1992), pages 5554 to 5556. In this case the PDI, at levels of between 3 and 4, is too high to be satisfactory.

EP-A 135 280 describes the use of stable N-oxyl radicals, which combine reversibly with the reactive chain ends. However, this process produces not high molecular mass-polymers but only oligomers instead.

U.S. Pat. No. 5,322,912 discloses cyclic, sterically shielded N-oxyl radicals which are used in combination with conventional initiators. These systems, however, do not permit the polymerization of alkyl acrylates.

EP-A 489 370 describes free-radically initiated addition polymerization in the presence of alkyl iodides. Here too, the molecular weights are at an unsatisfactorily low level.

The same disadvantage is shown by the products described in EP-A 222 619, which are prepared with the aid of bimetallic catalysts containing cyclopentadienyl ligands.

All methods known to date have the disadvantage that the additives used to control the reaction are very expensive and the processes are therefore uneconomic.

DETAILED DESCRIPTION OF THE INVENTION

It is an object of the present invention, therefore, to provide new processes for preparing polymers of vinylic monomers, which processes do not have the abovementioned disadvantages, can be applied to polar and apolar monomers, permit control of the molecular weight and of the molecular weight distribution, and are insensitive to small amounts of moisture.

We have found that this object is achieved by processes for preparing polymers of vinylic monomers, where polymerization is carried out in the presence of free-radical initiators and electron donors.

We have also found that the polymers obtainable in such processes can be used to prepare moldings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing TGA (Thermograph Analysis) curves for the poly(methyl methacrylate) of Example 2, below, and comparison Example 2C, below.

Particularly suitable vinylic monomers are vinylaromatic compounds such as styrene, 2-vinylnaphthalene and 9-vinylanthracene, substituted vinylaromatic compounds such as p-methylstyrene, a-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene and 4-vinylbiphenyl, C₁ - to C₈ -alkyl esters of acrylic or methacrylic acid, especially C₁ - to C₄ -acrylates and methacrylates, unsaturated dicarboxylic acids, for example aliphatic unsaturated dicarboxylic acids such as maleic or fumaric acid, or derivatives thereof such as anhydrides, esters and amides, especially anhydrides, such as maleic anhydride, or vinyl cyanides, especially acrylonitrile. Mixtures of different monomers can likewise be employed.

Preferred monomers are styrene, substituted styrenes, C₁ - to C₄ -acrylates and methacrylates, especially methyl methacrylate, and acrylonitrile.

The free-radical initiators employed in the novel process are known per se and are described, for example, in Ullmanns Encyclopadie der technischen Chemie, 4th edition, Volume 15, page 187. Particularly suitable initiators are peroxides, such as dibenzoyl peroxide and cumene hydroperoxide, and especially diazo compounds, such as azodiisobutyronitrile (AIBN). It is also possible to employ mixtures of different free-radical initiators. the molar amount of free-radical initiator can be from 10⁻⁶ to 1 mol/l, preferably from 10⁻⁴ to 10⁻¹ mol/l.

The novel process is also carried out in the presence of electron donors.

Electron donors are molecules which owing to mesomeric and/or inductive effects have an excess of π-electrons.

Examples of electron donors are compounds of the formula I or II ##STR1## where X is sulfur or selenium,

R¹ to R⁴ are hydrogen, C₁ - to C₂₀ -alkyl, preferably C₁ - to C₆ -alkyl, C₁ - to C₂₀ -alkoxy, preferably C₁ - to C₆ -alkoxy or C₆ - to C₁₈ -aryl, preferably phenyl

and

A is a double bond, ##STR2##

Preference is given to compounds of the formula I or II where R¹ and R² are identical and also R³ and R⁴ , or to those in which R¹ and R³ are identical and also R² and R⁴, i.e. symmetrical compounds. Preferably X is sulfur and R¹ to R⁴ are hydrogen or methyl. A particularly preferred compound is tetrathiafulvalene (TTF) ##STR3##

Further examples of electron donors are ##STR4## where X is sulfur or selenium and

R¹ to R⁴ are hydrogen, C₁ - to C₂₀ -alkyl, preferably C₁ - to C₆ -alkyl, C₁ - to C₂₀ -alkoxy, preferably C₁ - to C₆ -alkoxy or C₆ - to C₁₈ -aryl, preferably phenyl.

Here again, preference is given to the symmetrical compounds, i.e. to those in which either R¹ and R² and also R³ and R⁴ are identical or R¹ and R³ and also R² and R⁴. Here again, preferably, X is sulfur and R¹ to R⁴ are hydrogen or methyl.

Other electron donors which can be employed are compounds of the formula IX or X ##STR5## where Y is oxygen or sulfur,

R⁵ is C₁ - to C₂₀ -alkyl, preferably C₁ - to C₆ -alkyl, C₁ - to C₂₀ -alkoxy, preferably C₁ - to C₆ -alkoxy or C₆ - to C₁₈ -aryl, preferably phenyl,

and

n is an integer from 2 to 6.

Likewise suitable are phenoxazines, phenothiazine derivatives or phenoselenazines. ##STR6## where X is oxygen, sulfur or selenium, preferably sulfur, and

R⁶ is hydrogen, C₁ - to C₅ -alkyl, preferably methyl or ethyl, --CF₃, halogen, preferably --Cl, --CN, --SR^(a), --OR^(a) or --NR^(a) R^(b),

R^(a) is C₁ - to C₂₅ -alkyl, preferably C₁ - to C₂₂ -alkyl, especially C₁ - to C₁₀ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl, or C₆ - to C₁₈ -aryl, preferably phenyl,

R^(b) is hydrogen, C₁ - to C₂₅ -alkyl, preferably C₁ - to C₂₂ -alkyl, especially C₁ - to C₁₀ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl, C₆ - to C₁₈ -aryl, preferably phenyl,

R⁷ is hydrogen or .paren open-st.T.paren close-st.Z,

T is branched or unbranched C₁ - to C₂₅ -alkylene, preferably C₁ - to C₂₂ -alkylene and, with particular preference, C₁ - to C₁₀ -alkylene, for example methylene, ethylene, 2-methylethylene, n-propylene or n-butylene,

Z is --OH, --OR⁸, --SR⁸, --NR⁹ R¹⁰ or Q, among which --NR⁹ R¹⁰ or Q is preferred,

R⁸ is C₁ - to C₂₅ -alkyl, preferably C₁ - to C₂₂ -alkyl, especially C₁ - to C₁₀ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl, or C₆ - to C₁₈ -aryl, preferably phenyl,

R⁹ is hydrogen or C₁ - to C₂₅ -alkyl, preferably C₁ - to C₂₂ -alkyl, especially C₁ - to C₁₀ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl, or C₆ - to C₁₈ -aryl, preferably phenyl,

R¹⁰ is C₁ - to C₂₅ -alkyl, preferably C₁ - to C₂₂ -alkyl, especially C₁ - to C₁₀ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl, or C₆ - to C₁₈ -aryl, preferably phenyl,

where

R⁹ and R¹⁰, with one another and together with the nitrogen, can form a C₄ - to C₇ -cyclo-N-aliphatic ring, preferably a C₅ -cyclo-N-aliphatic or a C₆ -cyclo-N-aliphatic ring, which can be either unsubstituted or substituted by one or more C₁ - to C₅ -alkyls, preferably methyl, ethyl, n-propyl or isopropyl, and which can contain one or more, preferably one, --O--, --S-- or --N(R¹¹)--, the latter being preferred, where --O--, --S-- and --N(R¹¹)-- are not joined directly to one another,

Q is a C₄ - to C₇ -cycloaliphatic radical, preferably a C₅ - or C₆ -cycloaliphatic ring, which can contain one or more --O--, --S-- or --N(R¹¹)--, the latter being preferred, and where Q is in each case linked via a carbon to T and where --O--, --S-- and --N(R¹¹) are not joined directly to one another,

R¹¹ is C₁ - to C₁₀ -alkyl, preferably C₁ - to C₅ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl,

R¹² is hydrogen, C₁ - to C₂₀ -alkyl, preferably C₁ - to C₆ -alkyl or C₆ - to C₁₈ -aryl, preferably phenyl.

Preferred phenothiazines include: ##STR7## in each of which r is an integer from 2 to 11 and s is an integer from 1 to 4.

Further suitable electron donors are the following compounds: ##STR8## where X is sulfur or selenium, preferably sulfur

Y is oxygen or sulfur

R¹ to R⁴ are hydrogen, C₁ - to C₂₀ -alkyl, preferably C₁ - to C₆ -alkyl or C₆ - to C₁₈ -aryl, preferably phenyl

m is an integer from 0 to 4

q is an integer from 0 to 2

and

p is an integer from 2 to 100.

It is also possible to employ mixtures of different electron donors.

The compounds employed as electron donors are known per se or can be prepared by processes which are known per se and are described, for example, in J. H. Perlstein, Angew. Chem. Int. Ed. Engl. 16 (1977), pages 519 to 534 and M. R. Bryce, Aldrichimica Acta, Vol. 18 (1985), pages 73 to 77.

The molar ratio of electron donors to free-radical initiators can be in the range from 1:1 to 3:1, preferably from 1.6:1 to 2.4:1.

The conditions for the reaction are not critical; it can be carried out at from 0 to 220° C., preferably from 20 to 150° C., normally under atmospheric pressure, although it is also possible to operate at pressures up to 30 bar. The chosen reaction times are preferably such that polymerization is carried out until the desired molecular weight is reached, for example from 1 hour to 6 days.

The novel process can also be carried out in the presence of an organic solvent. Examples of suitable solvents are tetrahydrofuran (THF), toluene and ethylbenzene or mixtures thereof.

The novel process is preferably conducted by charging the free-radical initiator and the electron donor to the reactor and adding the monomer or monomers and, if used, the solvent. However, it is also possible to reverse the addition sequence. The polymers can be worked up by precipitation, for example from methanol or hexane.

The molecular weights Mn of the resulting polymers can vary within wide ranges, for example from 5000 to 500,000.

Particular features of the novel process are its economy: both polar and apolar monomers can be employed; its insensitivity to small amounts of moisture, and the possibility of reacting mixtures of monomers to give random copolymers. The resulting polymers have a PDI of less than 2, may have a high molecular weight, and exhibit relatively high thermal stability.

EXAMPLES

Examples 1 to 6

Preparing Polymethyl Methacrylate (PMMA)

Methyl methacrylate (MMA) was distilled over calcium hydride. THF and toluene were distilled over potassium and sodium, respectively. AIBN was recrystallized from methanol. Commercially available TTF was employed without additional purification.

The concentration of the monomers was 4.8 mol per liter of solvent. The free-radical initiator was employed in an amount of 2.4×10⁻² mol/l and the electron donor in an amount of 4.8×10⁻² mol/l. The polymerization reactions were conducted in a 50 ml Schlenk tube under argon. The monomer and the solvent were injected with a needle, through a septum, into the initial charge of free-radical initiator and electron donor in the argon-flushed Schlenk tube.

The polymer was worked up by precipitating the polymer solution, diluted with THF, from ten times the volume of methanol. The polymers prepared in toluene were precipitated from n-hexane.

The molecular weights were determined by GPC (gel permeation chromatography), with calibration using PMMA standards.

Comparison Examples C1 to C4

Preparing PMMA

Examples 1 to 6 were repeated but without adding TTF.

The reaction conditions and the properties of the polymethyl methacrylates are summarized in Table 1.

The thermal stability can be determined by thermogravimetric analysis (TGA). It was found that the temperature at which loss of mass begins is at markedly higher levels in the case of PMMA prepared by the novel process.

FIG. 1 shows the TGA curves of the PMMA from Example 2 and of the PMMA from Comparison Example C2, (N₂ atmosphere, heating rate 10 K/min).

                                      TABLE 1                                      __________________________________________________________________________                  Free-                                                               Experiment  radical Electron  Temp. Reaction                                   No. Monomer initiator donor Solvent [° C.] time Mn Mw PDI             __________________________________________________________________________     1      MMA   AIBN TTF  THF  60   72 h  21 500                                                                              31 800                                                                               1.48                           2 MMA AIBN TTF THF 60 72 h 31 500 46 000 1.46                                  3 MMA AIBN TTF THF 60 72 h 32 300 50 100 1.54                                  4 MMA AIBN TTF THF 60 72 h 31 500 48 400 1.53                                  5 MMA AIBN TTF Toluene 110  72 h 19 000 26 000 1.38                            6 MMA AIBN TTF Toluene 110  72 h 14 400 19 700 1.37                            C1 MMA AIBN -- THF 60 24 h 51 300 103 100  2.01                                C2 MMA AIBN -- THF 60 24 h 34 000 70 000 2.06                                  C3 MMA AIBN -- Toluene 110  24 h  7 700 35 800 4.65                            C4 MMA AIBN -- Toluene 110  24 h  5 600 28 500 5.03                          __________________________________________________________________________

Examples 7 to 10

Preparing Polystyrene

Examples 1 to 6 were repeated but using styrene as monomer instead of MMA.

Comparison Examples C5 to C8

Preparing Polystyrene

Examples 7 to 10 were repeated but without adding TTF.

The reaction conditions and the properties of the polystyrenes are summarized in Table 2.

                                      TABLE 2                                      __________________________________________________________________________                  Free-                                                               Experiment  radical Electron  Temp. Reaction                                   No. Monomer initiator donor Solvent [° C.] time Mn Mw PDI             __________________________________________________________________________      7     Styrene                                                                              AIBN TTF  THF  60   72 h  14 200                                                                              25 400                                                                               1.78                            8 Styrene AIBN TTF THF 60 72 h 16 300 29 000 1.77                              9 Styrene AIBN TTF Toluene 110  72 h  9 200 15 400 1.67                       10 Styrene AIBN TTF Toluene 110  72 h 13 800 25 600 1.85                       C5 Styrene AIBN -- THF 60 24 h 10 600 28 400 2.68                              C6 Styrene AIBN -- THF 60 24 h 10 800 28 000 2.59                              C7 Styrene AIBN -- Toluene 110  24 h 16 700 63 500 3.78                        C8 Styrene AIBN -- Toluene 110  24 h 15 500 55 500 3.56                      __________________________________________________________________________

Example 11

Preparing a Copolymer of MMA and Styrene

Examples 1 to 6 were repeated but employing MMA and styrene as monomers (molar ratio 1:1).

The reaction conditions and the properties of the copolymer are summarized in Table 3.

                                      TABLE 3                                      __________________________________________________________________________                  Free-                                                               Experiment  radical Electron  Temp. Reaction                                   No. Monomer initiator donor Solvent [° C.] time Mn Mw PDI             __________________________________________________________________________       11 Styrene/ AIBN TTF THF 60 72 h 21 100 32 000 1.51                             MMA                                                                         __________________________________________________________________________

Examples 12 to 14

Preparing Polystyrene and Styrene-Acrylonitrile Copolymers Using Phenothiazines as Electron Donor

Examples 1 to 6 were repeated but using commercially available phenothiazine (V, R⁶, R⁷ ═H) (PTA) and dimethylaminopropylphenothiazine (V, R⁶ ═H, R⁷ ═--CH₂ --CH(CH₃)--N(CH₃)₂) (DMAPPTA) as electron donors. The monomers used were styrene and, respectively, a mixture of styrene and acrylonitrile (AN) (weight ratio 3:1). Commercially available benzoyl peroxide, which was employed without additional purification, served as the free-radical initiator. The benzoyl peroxide and the electron donor were employed in equimolar amounts. The concentration of the benzoyl peroxide relative to monomer was 0.1 mol %.

The reaction conditions and the properties of the resulting polymers and copolymers are given in Table 4.

                                      TABLE 4                                      __________________________________________________________________________                  Free-                                                               Experiment  radical Electron  Temp. Reaction                                   No. Monomer initiator donor Solvent [° C.] time Mn Mw PDI             __________________________________________________________________________     12     Styrene                                                                              BPO  PTA    THF  130   2 h  178 600                                                                             300 000                                                                             1.68                          13 Styrene BPO DMAPPTA THF 130 25 h  76 500 193 600 2.53                       14 Styrene/ BPO PTA THF 130  1 h  28 600  83 000 2.9                            AN                                                                            C9 Styrene BPO -- THF 130  2 h  71 200 192 300 2.7                              C10 Styrene/ BPO -- THF 130  1 h  2 900  40 000 14                             AN                                                                          __________________________________________________________________________

Example 15

Changing the Molecular Weight With Time

Example 12 was repeated except that a smaller proportion of BPO and PTA to styrene was chosen (0.29 g of BPO, 0.18 g of PTA, 104.15 g of styrene). At the intervals shown below samples were taken, the products were precipitated from methanol and the precipitates were collected, dried under reduced pressure at 80° C. and analyzed. The results are shown in Table 5:

                  TABLE 5                                                          ______________________________________                                         Time         M.sub.n    M.sub.w PDI                                            ______________________________________                                         30 min       57 600     144 000 2.5                                              60 min 69 000 173 000 2.5                                                      3 h 90 200 198 000 2.2                                                         5 h 88 800 213 000 2.4                                                       ______________________________________                                    

Table 5 shows that the molecular weight increases the longer the reaction time. 

We claim:
 1. A process for preparing addition polymers of vinylic monomer selected form the group consisting of vinylaromatic compounds substituted vinylaromatic compounds, C₁ - to C₈ -alkyl esters of acrylic or methacrylic acid unsaturated dicarboxylic acids or their derivatives, vinyl cyanides, and mixtures thereof, having a PDI of less than 2, which comprises carrying out the polymerization in the presence of free-radical initiators and of electron donors of the formula I or II ##STR9## where x is sulfur or seleniumR¹ to R⁴ hydrogen, C₁ - to C₂₀ -alkyl, C₁ - to C₂₀ -alkoxy or C₆ - to C₁₈ -aryland A is a double bond, ##STR10## or of the formulae III to VIII ##STR11## where X is sulfur or selenium, R¹ to R⁴ are hydrogen, C₁ - to C₂₀ -alkyl, C₁ - to C₂₀ -alkoxy or C₆ - to C₁₈ -aryl, or of the formula IX or X ##STR12## where X is oxygen or sulfur,and R⁶ is hydrogen, C₁ - to C₅ -alkyl, --CF₃, halogen, --CN, --SR^(a), --OR^(a) or NR^(a) R^(b), R^(a) is C₁ - to C₂₅ -alkyl or C₆ - to C₁₈ -aryl, R^(b) is hydrogen, C₁ - to C₂₅ -alkyl or C₆ - to C₁₈ -aryl, R⁷ is hydrogen or (T)Z, T is branched or unbranched C₁ - to C₂₅ -alkylene, Z is --OH, --OR⁸, --SR⁸, --NR⁹ R¹⁰ or Q R⁸ is C₁ - to C₂₅ -alkyl or C₆ -C₁₈ -aryl, R⁹ is hydrogen or C₁ - to C₂₅ -alkyl or C₆ - to C₁₈ -aryl, R¹⁰ is C₁ - to C₂₅ -alkyl or C₆ - to C₁₈ -aryl,where R⁹ and R¹⁰, with one another and together with the nitrogen, can optionally form a C₄ - to C₇ -cyclo-N-aliphatic ring which can be either unsubstituted or substituted by one or more C₁ -to C₅ -alkyls and can contain one or more --O--, --S-- or --N(R¹¹)--, where --O--, --S-- and --N(R¹¹)-- are not joined directly to one another, Q is a C₄ - to C₇ -cycloaliphatic radical which optionally contains one or more --O--, --S-- or --N(R¹¹)--, and where Q is in each case linked via a carbon to T and where --O--, --S-- and --N(R¹¹)--, are not joined directly to one another, R¹¹ is C₁ - to C₁₀ -alkyl, R₁₂ is hydrogen, C₁ - to C₂₀ -alkyl or C₆ - to C₁₈ -aryl.
 2. A process as claimed in claim 1, wherein said vinylic monomers are selected from the group consisting of styrene, substituted styrene, C₁ - to C₄ alkyl esters of acrylic or methacrylic acid, acrylonitrile, and mixtures thereof.
 3. A process as claimed in claim 1 wherein the electron donor is a phenoxazine, phenothiazine, or phenoselazine derivative of formula XI or XII.
 4. A process as claimed in claim 1, wherein the electron donor employed is tetrathiafulvalene ##STR13##
 5. A process as claimed in claim 1, which is carried out in an organic solvent.
 6. A process as claimed in claim 1, wherein the molar ratio of electron donors to free-radical initiators is in the range from 1:1 to 3:1.
 7. The process of claim 2, wherein said electron donor is a phenoxazine, phenothiazine, or phenoselazine derivative of formula XI or XII.
 8. The process of claim 2, wherein said electron donor is tetrathiafulvalene ##STR14##
 9. A process as claimed in claim 2, which is carried out in a solvent.
 10. A process as claimed in claim 2, wherein the molar ratio of electron donors to free-radical initiators is in the range from 1:1 to 3:1.
 11. A process as claimed in claim 7, which is carried out in a solvent.
 12. A process as claimed in claim 7, wherein the molar ratio of electron donors to free-radical initiators is in the range from 1:1 to 3:1.
 13. A process as claimed in claim 8, which is carried out in a solvent.
 14. A process as claimed in claim 8, wherein the molar ratio of electron donors to free-radical initiators is in the range from 1:1 to 3:1.
 15. A process for preparing addition polymers of vinylic monomers selected from the group consisting of vinylaromatic compounds, substituted vinylaromatic compounds, C₁ - to C₈ -alkyl esters of acrylic or methacrylic acid, unsaturated dicarboxylic acids or their derivatives, vinyl cyanides, and mixtures thereof, having a PDI of less than 2, which comprises carrying out the polymerization in the presence of free-radical initiators and of electron donors of the formula I or II whereX is sulfur or selenium R¹ to R⁴ hydrogen, C₁ - to C₂₀ -alkyl, C₁ - to C₂₀ -alkoxy or C₆ - to C₁₈ -aryland A is a double bond, ##STR15## or of the formulae III to VI ##STR16## where X is sulfur or selenium, R¹ to R⁴ are hydrogen, C₁ - to C₂₀ -alkyl, C₁ - to C₂₀ -alkoxy or C₆ - to C₁₈ -aryl, or of the formula XI or XII ##STR17## where X is sulfur or seleniumand R⁶ is hydrogen, C₁ - to C₆ -alkyl, --CF₃, halogen, --CN, --SR^(a), --OR^(a) or NR^(a) R^(b), R^(a) is C₁ - to C₂₅ -alkyl or G₆ - to C₁₈ -aryl, R^(b) is hydrogen, C₁ - to C₂₅ -alkyl or C₆ - to C₁₈ -aryl, R⁷ is hydrogen or (T)Z, T is branched or unbranched C₁ - to C₂₅ -alkylene, Z is --OH, --OR⁸, --SR⁸, --NR⁹ R¹⁰ or Q R⁸ is C₁ - to C₂₅ -alkyl or C₆ -C₁₈ -aryl, R⁹ is hydrogen or C₁ - to C₂₅ -alkyl or C₆ - to C₁₈ -aryl, R¹⁰ is C₁ - to C₂₅ -alkyl or C₆ - to C₁₈ -aryl,where R⁹ and R¹⁰, with one another and together with the nitrogen, can optionally form a C₄ - to C₇ -cyclo-N-aliphatic ring which can be either unsubstituted or substituted by one or more C₁ - to C₅ -alkyls and can contain one or more --O--, --S-- or --N(R¹¹)--, where --O--, --S-- and --N(R¹¹)-- are not joined directly to one another, Q is a C₄ - to C₇ -cycloaliphatic radical which optionally contains one or more --O--, --S-- or --N(R¹¹)--, and where Q is in each case linked via a carbon to T and where --O--, --S-- and --N(R¹¹)--, --O--, --S-- and --N(R¹¹)-- are not joined directly to one another, R¹¹ is C₁ - to C₁₀ -alkyl, R₁₂ is hydrogen, C₁ - to C₂₀ -alkyl or C₆ - to C₁₈ -aryl.
 16. The process of claim 15, wherein said vinylic monomers are selected from the group consisting of styrene, substituted styrene, C₁ -C₄ -alkyl esters of acrylic or methacrylic acid, acrylonitrile, or mixtures thereof.
 17. A process as claimed in claim 15, wherein the molar ratio of electron donors to free-radical initiators is in the range from 1:1 to 3:1.
 18. A process as claimed in claim 15, which is carried out in a solvent.
 19. A process as claimed in claim 16, which is carried out in a solvent.
 20. A process as claimed in claim 16, wherein the molar ratio of electron donors to free-radical initiators is in the range from 1:1 to 3:1. 